Method for imparting antimicrobic properties to polyvinyl alcohol articles



United States Patent 3,390,008 METHOD FOR IMPARTING ANTIMICROBIC PROPERTIES TO POLYVINYL ALCOHOL ARTICLES Solomon Aronovich Giller, Pernavas 10, Apt. 76, Riga,

U.S.S.R., and Leonard Abramovich Wolf, Nevsky Prospect 16, Apt. 11, and Alexander Ivanovich Meos, Chaikovsky Str. 43, Apt. 2, both of Leningrad, U.S.S.R. N0 Drawing. Filed Nov. 7, 1963, Ser. No. 322,042 12 Claims. (Cl. 117-1385) ABSTRACT OF THE DISCLOSURE The modification of fibers or films of polyvinyl alcohol by treatment with a S-nitrofuran compound to impart antimicrobic and antimycotic properties to the polyvinyl alcohol fibers or films.

This invention relates to a method of producing polyvinyl alcohol fibres or films with inherent antimicrobic and antimycotic properties resulting from a permanent chemical bond between polyvinyl alcohol and pharmaceutical compounds of the S-nitrofuran series. It is well known that nitrofuran derivatives widely used for medical preparations exert a strong antibacterial activity and by way of chemical bonds might possibly impart this property to the polyvinyl alcohol products. Thus, the latter themselves could be transformed into self-acting antibiotics. Our practical aim is to produce a synthetic product of polyvinyl alcohol with inherent antimicrobic properties in order to manufacture a number of articles biologically active by themselves and destined to be used for medical and sanitary purposes.

The problem of the creation of fibres capable of killing pathogenic bacteria has up to now been solved in a single direction, namely, by impregnating the fibre with disinfectants. It is known that during World War II the uniforms of some German soldiers were impregnated by quaternary ammonium base compounds. It is known also that these persons suffered much less from secondary infections (accompanying combat wounds and infections) than those whose uniforms were not impregnated with the disinfectants.

In the U.S.A. impregnation of bedding, diapers, dressing, towels etc. with quaternary ammonium bases is practised when treating patients, especially children. In Great Britain it has been proposed to treat woolen blankets, mattress covers and other textile pieces with antiseptics.

Various papers which have been published recently on the impregnation of fibres with appropriate reagents as well as on the evaluation of methods for analysing antibacterial activity of these fibres, testify to the outstanding consideration given to deriving fibres with residual antibacterial activity.

Thus, we take into account that prior to our invention there were methods of imparting residual antibacterial activity to fibres by impregnating fibres and fabrics with the appropriate disinfectants (for example, with quaternary ammonium, organo-tin, phenolic and other compounds).

But the general shortcoming of the previous solutions lies in the fact that all of them require fibre impregnation. Whereas, the application of appropriate reagents to the fibre without being bound there with a chemical bond is accompanied by a number of technical and economical inconveniences. The service life of such articles is extremely limited, while their antibacterial properties are actually destroyed in the first washing (since in this case the impregnating compounds are washed off from the fibre).

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It is preferable, therefore, to have such antimicrobic fibres which would possess groups providing antibacterial activity in their own structure, i.e., in other words, it is desirable to provide the chemical bond between fibres and bactericidal active substances. In this case, the antibacterial activity of the fibre does not disappear during the use of the articles and is retained in practice during their whole life.

Prior to the instant invention we have tried to derive this type of fibre by treating the fibre of polyvinyl alcohol with solutions of molecular iodine. These experiments resulted in the obtainment of polyvinyl alcohol fibres with a residual .antibacterial effect. In this case, however, the chemical bond between the fibre and the iodine did not take place since their interaction is of the iodine sorption by the fibre. Due to this the iodine is easily Sublimated and is washed off from the fibre causing the disappearance of the antibacterial effect of polyvinyl alcohol molecules. Thus, the said method of fibre treatment with the antiseptic may be included among the series of methods of fibre impregnation with antibacterial preparations.

To our knowledge, no other attempts in deriving fibres with a chemical bond between the fibre and the bactericidal active substances have been made prior to our invention.

It is now ascertained that the method proposed by us excludes that of impregnation used before it, and produces fibres possessing antibacterial as well as antimycotic activity.

The general idea of said method consists in deriving a fibre possessing antibacterial and antimycotic activity by binding the appropriate bactericidal active reagents on them by means of a chemical bond.

In principle, the antimicrobic and antimycotic properties can be imparted to by any polymer which possesses reactive functional groups. We have chosen polyvinyl alcohol materials as they have very high strength indices. Owing to this advantage we have chosen the polyvinyl alcohol fibre as an object for deriving the biologically active fibres.

The said idea is realized by adding the groups providing antibacterial activity of medical preparations, for example, the nitrofuranic group comprised in the chemotherapeutic substances of the nitrofuran series (such as furacilin, furadonin, furazolidon and others) being responsible for the development of bacteriostatic activity by these compoundsto the macromolecules of the polymer (fibre or film). For example, S-nitrofurfural, S-nitrofurylacrolein, their diacetates, etc. may be used for this purpose.

One or other reagents imparting the antibacterial and antimycotic properties to the fibre are chosen in each case in conformity with the particular requirement (including the textile indices) to the derived samples of fibres with biological activity.

The object of the invention is to derive fibres (films) and on the basis of the latter-the articles possessing biological activity, i.e. the ability to kill pathogenic bacteria, as well as fungi, and may be used in this connection for the following purposes:

(a) As a packing material and dressing having reliable sterility and bactericidal properties;

(b) As bactericidal surgical threads for suturing wounds;

(c) As antiseptic bed-clothes and underclothes (especially for new-born children) as well as an overalls for medical personnel and others;

(d) As stockings, socks, gloves, hats, inner soles and other materials which may be used for prophylactic measures against fungus diseases;

(e) As antimicrobic filters to disinfect water, including peat water.

In conformity with the above-said and other objects the Example 1.Treatment with 5nitrofurylacrolein The polyvinyl alcohol fibre is heated in the air (thermal stabilization) at a temperature of 2l0220 C. for 7-10 min. and then treated in a bath containing 5-nitrofurylacrolein (2 percent), sulfuric acid (20 percent), 60 percent ethyl (or methyl) alcohol (78 percent) for 35 hours at a temperature of 70 C., the goods-liquor ratio equalling 1:40.

Example 2 Treatment with S-nitrofurfural after the thermostabilization described in Example 1 the polyvinyl alcohol fibre is treated in a bath of the following contents: 5- nitrofurfural (2 percent), sulfuric acid (20 percent), 50 percent ethyl (or methyl) alcohol (78 percent); the fibre is treated for 3-5 hours at a temperature of 70 C., the goods-liquor ratio being 1:40.

Table 1 shows the basic textile indices of fibres derived in conformity with the said mixing formula of fibres.

TABLE 1 Acetalating agent Physical and mechanical indices S-nitrofuryl- 5-nitroiuracrolein fural Strength of single fibre, km. of disruptivc length 19. 7 22. 4 Elongation, percent a. 45. 43. 0

Shrinkage alter boi g water for 1 hour, percent 4. 8 4. 6

Table 2 presents the quantitative characteristic of antibacterial activity developed by these fibres.

TABLE 2 Aeetalating agent fi-nitrofuryl- Antibacterial effect -nitrofuriural acrolein Amount of meat-peptone broth wherein 1 g. of fibre completely suppresses the staphylococcus growth, In] 2, 000 100 Zone of inhibition of staphylococcus growth on agar by 10 mg. of fibre,

mm 18 12 The same for the Escherichia colt, mm" 16 10 The zone of inhibition of the test-cultures growth on the agar comprises also the 10 mm. diameter of the recess holding the fibre.

The fibres possess also antimycotic properties, in particular, relative to the trichophyton-gypseum and the Kaufmann-Wolf epidermophyton.

Example 3.Treatment with diacetates of aldehydes of nitrofuran series The thermostabilized polyvinyl alcohol fibre is treated (as was indicated in Example 1) in a water bath containing 4 percent of nitrofurfural or nitrofurylacrolein diacetate and 20 percent of sulfuric acid at a temperature 4 of 80 C. for 3-5 hours; the ratio of goods to liquor being 1:80.

The obtained samples possess antibacterial activity, but their quantitative characteristics are as yet not determined.

What we claim is:

1. A process for imparting antimicrobic properties to articles which comprises acetalizing the polyvinyl alcohol articles with a 5-nitrofuran compound whereby the S- nitrofuran compound is chemically bonded to the polyvinyl alcohol.

2. A process as claimed in claim 1 wherein the polyvinyl alcohol articles are thermally stabilized prior to the acetalizing.

3. The process of claim 1 wherein the compound is 8-5-nitrofurylacrolem.

4. The process of claim 1 wherein the compound is S-nitrofurfural.

5. The process of claim 1 wherein the S-nitrofuran compound is an acetate of the 5-nitrofuran series.

6. The process of claim 5 wherein the acetate is 5- nitrofurfural diacetate.

7. The process of claim 1 wherein the acetalizing is carried out in a bath consisting essentially of sulfuric acid and an alcohol selected from the group consisting of methanol or ethanol.

8. The process of claim 1 wherein the acetalizing is carried out at a temperature of about between and C.

9. Process of claim 7 wherein said bath has a composition containing about 2% S-nitrofurylacrolein, 20% sulfuric acid and of an alcohol selected from a group consisting of 78% ethanol or methanol for 35 hours at about 70 C.

10. Process of claim 7 wherein the said bath has a composition containing about 2% S-nitrofurfural, about 20% sulfuric acid, about 78% of an alcohol selected from a group consisting of ethanol or methanol for 35 hours at about 70 C.

11. Process of claim 7 wherein the said bath has a composition containing about 4% of S-nitrofuran derivatives selected from a group consisting of 5-nitrofurfural or S-nitrofurylacrolein diacetate and about 20% sulfuric acid for between about 3 to 5 hours at about 80 C.

12. Polyvinyl alcohol products selected from a group consisting of polyvinyl alcohol article modified by a S-nitrofuran compound and having antimicrobic properties when produced by the process of claim 1.

References Cited UNITED STATES PATENTS Cottet et a1. 2601l5.5 X

WILLIAM D. MARTIN, Primary Examiner.

T. G. DAVIS, Assistant Examiner. 

